Dye composition using at least one coupler of meta-phenylenediamine type substituted in position 2 in a medium comprising a fatty substance, processes and device

ABSTRACT

The present invention relates to a composition for dyeing keratin fibers, in particular human keratin fibers, comprising one or more fatty substances, one or more surfactants, one or more oxidation bases, one or more particular couplers of meta-phenylenediamine type substituted in position 2, and one or more basifying agents, the fatty substance content in the dye composition representing in total at least 5% by weight relative to the total weight of the said composition. The invention also relates to a dyeing process using such a composition, and also to multi-compartment devices suitable for performing the said process.

The present invention relates to a composition for dyeing keratinfibres, in particular human keratin fibres such as the hair, comprisingone or more fatty substances, one or more surfactants, one or moreoxidation bases, one or more particular couplers ofmeta-phenylenediamine type substituted in position 2, and one or morebasifying agents, the fatty substance content in the dye compositionrepresenting in total at least 15% by weight relative to the totalweight of the said composition.

The invention also relates to a process for dyeing keratin fibres usingthe said composition in the presence of one or more chemical oxidizingagents, and also to a multi-compartment device suitable for using thesaid dye composition.

Many people have sought for a long time to modify the colour of theirhair and in particular to mask their grey hair.

It is known practice to dye keratin fibres, and in particular humankeratin fibres such as the hair, in order to obtain “permanent”colorations with dye compositions containing oxidation dye precursors,which are generally known as oxidation bases, such as ortho- orpara-phenylenediamines, ortho- or para-aminophenols or heterocycliccompounds such as pyrazoles, pyrazolinones or pyrazolopyridines. Theseoxidation bases are colourless or weakly coloured compounds which, incombination with oxidizing products, can give rise to coloured compoundsby an oxidative condensation process.

It is also known that the shades obtained with these oxidation bases maybe varied by combining them with couplers or coloration modifiers, thelatter being chosen especially from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compoundssuch as indole or pyridine compounds. The variety of molecules used asoxidation bases and couplers allows a wide range of colours to beobtained.

The oxidation dyeing process thus consists in applying to keratin fibresa dye composition comprising oxidation bases or a mixture of oxidationbases and couplers with hydrogen peroxide (H₂O₂ or aqueous hydrogenperoxide solution), as oxidizing agent, in leaving it to diffuse, andthen in rinsing the fibres.

However, the use of these dye compositions may present a certain numberof drawbacks. Specifically, after application to keratin fibres, thedyeing power obtained may not be entirely satisfactory, or even poor,and lead to a restricted range of colours. The colorations may also notbe sufficiently remanent with respect to external agents such as light,shampoo or perspiration, and may also be too selective, i.e. thecoloration difference is too great along the same keratin fibre that isdifferently sensitized between its end and its root.

One of the objects of the present invention is especially to proposecompositions for dyeing keratin fibres, in particular human keratinfibres such as the hair, which are especially capable of leading to awide range of colours with colorations that are powerful, sparinglyselective and remanent with respect to external agents (such as shampoo,light, perspiration or bad weather).

This aim is achieved by the present invention, one subject of which isespecially a composition for dyeing keratin fibres, in particular humankeratin fibres such as the hair, comprising:

-   -   (i) one or more fatty substances,    -   (ii) one or more surfactants,    -   (iii) one or more oxidation bases,    -   (iv) one or more basifying agents,    -   (v) one or more meta-phenylenediamine-based couplers of formula        (I), and also the addition salts thereof, optical isomers,        geometrical isomers and tautomers thereof and/or solvates        thereof:

-   -   in which formula (I):        -   R₁ is a linear or branched C₁-C₆ alkyl radical, which may be            substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHCOCH₃ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,        -   R₂ represents:        -    a hydrogen atom;        -    a linear or branched C₁-C₆ alkyl radical, which may be            substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,            -   C₁-C₆ alkoxy radicals,        -    a linear or branched C₁-C₆ alkoxy radical, which may be            substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,            -   C₁-C₆ alkoxy radicals,        -    a halogen radical,        -   R₃ and R₄ represent, independently of each other:        -    a hydrogen atom,        -    a linear or branched C₁-C₆ alkyl radical, which may be            substituted with one or more of the following:            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   C₁-C₆ alkoxy radicals,        -   X represents an oxygen or sulfur atom,        -   n represents an integer ranging from 0 to 2,    -   (vi) one or more chemical oxidizing agents,    -   the fatty substance content representing in total at least 15%        by weight relative to the total weight of the said dye        composition.

Thus, the couplers used in the dye composition are chosen from themeta-phenylenediamines of formula (I).

The dye compositions make it possible to obtain colorations that arepowerful, sparingly selective and remanent with respect to externalagents (such as shampoo, light, perspiration or bad weather).

Moreover, the dye compositions according to the present invention allowa wide range of colours to be obtained.

Other subjects, characteristics, aspects and advantages of the presentinvention will emerge even more clearly on reading the description andthe examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of arange of values are included in that range.

The expression “at least one” is equivalent to the expression “one ormore”.

In general, the term “addition salts” of compounds means the additionsalts of these compounds with an acid, such as hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates,tosylates, benzenesulfonates, dodecylbenzenesulfonates, phosphates andacetates, and preferably the hydrochlorides, citrates, succinates,tartrates, phosphates and lactates.

The solvates of compounds more particularly represent the hydrates ofsuch compounds and/or the combination of such compounds with a linear orbranched C₁-C₄ alcohol such as methanol, ethanol, isopropanol orn-propanol. Preferably, the solvates are hydrates.

Fatty Substances:

As it has been mentioned, the composition of the invention comprises atleast one fatty substance.

The term “fatty substance” means an organic compound that is insolublein water at ordinary temperature (25° C.) and at atmospheric pressure(760 mmHg or 1.013×10⁵ Pa) (solubility of less than 5%, preferably ofless than 1% and even more preferentially of less than 0.1%). They havein their structure at least one hydrocarbon-based chain containing atleast 6 carbon atoms or a sequence of at least two siloxane groups. Inaddition, the fatty substances are generally soluble in organic solventsunder the same temperature and pressure conditions, for instancechloroform, dichloromethane, carbon tetrachloride, ethanol, benzene,toluene, tetrahydrofuran (THF), liquid petroleum jelly ordecamethylcyclopentasiloxane.

The fatty substances of the invention do not contain salified carboxylicacid groups.

In addition, the fatty substances of the invention are not(poly)oxyalkylenated or (poly)glycerolated ethers.

The term “oil” means a “fatty substance” that is liquid at roomtemperature (25° C.) and at atmospheric pressure (760 mmHg or 1.013×10⁵Pa).

The term “non-silicone oil” means an oil not containing any siliconatoms (Si) and the term “silicone oil” means an oil containing at leastone silicon atom.

More particularly, the fatty substance(s) are chosen from C₆-C₁₆hydrocarbons, hydrocarbons containing more than 16 carbon atoms,non-silicone oils of animal origin, triglycerides of plant or syntheticorigin, fluoro oils, fatty alcohols, fatty acid and/or fatty alcoholesters other than triglycerides and non-silicone waxes, in particularplant waxes, non-silicone waxes, and silicones, and mixtures thereof.

It is recalled that the fatty alcohols, esters and acids moreparticularly have at least one linear or branched, saturated orunsaturated hydrocarbon-based group comprising 6 to 30 and better stillfrom 8 to 30 carbon atoms, which is optionally substituted, inparticular with one or more hydroxyl groups (in particular 1 to 4). Ifthey are unsaturated, these compounds can comprise one to threeconjugated or non-conjugated carbon-carbon double bonds.

The linear or branched hydrocarbons of mineral or synthetic origincontaining more than 16 carbon atoms are preferably chosen from liquidparaffins, petroleum jelly, liquid petroleum jelly, polydecenes andhydrogenated polyisobutene such as Parleam®, and mixtures thereof.

As regards the C₆-C₁₆ hydrocarbons, they are more particularly linear,branched or optionally cyclic, and are preferably alkanes. Examples thatmay be mentioned include hexane, cyclohexane, undecane, dodecane,tridecane or isoparaffins, such as isohexadecane, isodecane orisododecane, and mixtures thereof.

As hydrocarbon-based oils of animal origin, mention may be made ofperhydrosqualene.

The triglycerides of vegetable or synthetic origin are preferably chosenfrom liquid fatty acid triglycerides comprising from 6 to 30 carbonatoms, for instance heptanoic or octanoic acid triglycerides, oralternatively, more particularly from those present in plant oils, forinstance sunflower oil, corn oil, soybean oil, marrow oil, grapeseedoil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, araraoil, castor oil, avocado oil, jojoba oil, shea butter oil or syntheticcaprylic/capric acid triglycerides, for instance those sold by thecompany Stéarineries Dubois or those sold under the names Miglyol® 810,812 and 818 by the company Dynamit Nobel, and mixtures thereof.

Fluoro oils that may be mentioned include perfluoromethylcyclopentaneand perfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1and Flutec® PC3 by the company BNFL Fluorochemicals;perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such asdodecafluoropentane and tetradecafluorohexane, sold under the names PF5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold underthe name Foralkyl® by the company Atochem; nonafluoromethoxybutane andnonafluoroethoxyisobutane; perfluoromorpholine derivatives such as4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® bythe company 3M.

The fatty alcohols that are suitable for the implementation of theinvention are more particularly chosen from saturated or unsaturated andlinear or branched alcohols comprising from 6 to 30 carbon atoms andpreferably from 8 to 30 carbon atoms. Examples that may be mentionedinclude cetyl alcohol, isostearyl alcohol, stearyl alcohol and themixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol,2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol, linolenyl alcohol,ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, andmixtures thereof.

As regards the fatty acid and/or fatty alcohol esters other than thetriglycerides mentioned above and non-silicone waxes, mention may bemade especially of esters of saturated or unsaturated, linear C₁-C₂₆ orbranched C₃-C₂₆ aliphatic monoacids or polyacids and of saturated orunsaturated, linear C₁-C₂₆ or branched C₃-C₂₆ aliphatic monoalcohols orpolyalcohols, the total carbon number of the esters being greater thanor equal to 6 and more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate;octyldodecyl behenate; isocetyl behenate; cetyl lactate; C₁₂-C₁₅ alkyllactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyllactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate;cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate;isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononylisononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristylstearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate;octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate;ethyl and isopropyl palmitates; 2-ethylhexyl palmitate, 2-octyldecylpalmitate, alkyl myristates such as isopropyl, butyl, cetyl,2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butylstearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyllaurate, and mixtures thereof.

Still within the context of this variant, esters of C₄-C₂₂ dicarboxylicor tricarboxylic acids and of C₁-C₂₂ alcohols and esters of mono-, di-or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- or pentahydroxyalcohols may also be used.

Mention may in particular be made of: diethyl sebacate; diisopropylsebacate; diisopropyl adipate; di(n-propyl) adipate; dioctyl adipate;diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate; tridecylerucate; triisopropyl citrate; triisostearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisononanoate; and polyethylene glycol distearates,and mixtures thereof.

Among the esters mentioned above, use is preferably made of ethyl,isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates, such as isopropyl, butyl,cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate,isobutyl stearate, dioctyl malate, hexyl laurate, 2-hexyldecyl laurate,isononyl isononanoate or cetyl octanoate, and mixtures thereof.

The composition may also comprise, as fatty ester, sugar esters anddiesters of C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. It should beremembered that the term “sugar” means oxygen-comprisinghydrocarbon-based compounds bearing several alcohol functions, with orwithout aldehyde or ketone functions, and which comprise at least 4carbon atoms. These sugars may be monosaccharides, oligosaccharides orpolysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (orsaccharose), glucose, galactose, ribose, fucose, maltose, fructose,mannose, arabinose, xylose and lactose, and derivatives thereof,especially alkyl derivatives, such as methyl derivatives, for instancemethylglucose.

The sugar esters of fatty acids may be chosen especially from the groupcomprising the esters or mixtures of esters of sugars describedpreviously and of linear or branched, saturated or unsaturated C₆-C₃₀and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, thesecompounds may comprise one to three conjugated or unconjugatedcarbon-carbon double bonds.

The esters according to this variant can also be chosen from mono-, di-,tri- and tetraesters, polyesters and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates,myristates, behenates, cocoates, stearates, linoleates, linolenates,caprates, arachidonates or mixtures thereof, such as, in particular,oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of monoesters and diesters and inparticular mono- or di-oleate, -stearate, -behenate, -oleopalmitate,-linoleate, -linolenate or -oleostearate of sucrose, of glucose or ofmethylglucose.

An example that may be mentioned is the product sold under the nameGlucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of esters of sugar and of fatty acid thatmay also be mentioned include:

-   -   the products sold under the names F160, F140, F110, F90, F70 and        SL40 by the company Crodesta, respectively denoting sucrose        palmitate/stearates formed from 73% monoester and 27% diester        and triester, from 61% monoester and 39% diester, triester and        tetraester, from 52% monoester and 48% diester, triester and        tetraester, from 45% monoester and 55% diester, triester and        tetraester, from 39% monoester and 61% diester, triester and        tetraester, and sucrose mono laurate;    -   the products sold under the name Ryoto Sugar Esters, for example        referenced B370 and corresponding to sucrose behenate formed        from 20% monoester and 80% diester-triester-polyester;    -   the sucrose mono-dipalmitate/stearate sold by the company        Goldschmidt under the name Tegosoft® PSE.

The non-silicone wax(es) are especially chosen from carnauba wax,candelilla wax, esparto wax, paraffin wax, ozokerite, plant waxes, suchas olive tree wax, rice wax, hydrogenated jojoba wax or absolute flowerwaxes, such as the blackcurrant blossom essential wax sold by thecompany Bertin (France), or animal waxes, such as beeswaxes or modifiedbeeswaxes (cerabellina); other waxes or waxy starting materials that maybe used according to the invention are in particular marine waxes, suchas that sold by the company Sophim under the reference M82, polyethylenewaxes or polyolefin waxes in general.

The silicones that may be used in the dye composition of the presentinvention are volatile or non-volatile, cyclic, linear or branchedsilicones, which are unmodified or modified by organic groups, having aviscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., and preferably 1×10⁻⁵ to 1m²/s.

The silicones that may be used in accordance with the invention may bein the form of oils, waxes, resins or gums.

Preferably, the silicone(s) are chosen from polydialkylsiloxanes, inparticular polydimethylsiloxanes (PDMSs), and organomodifiedpolysiloxanes comprising at least one functional group preferably chosenfrom amino groups and alkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll'sChemistry and Technology of Silicones (1968), Academic Press. They maybe volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen fromthose having a boiling point of between 60° C. and 260° C., and evenmore particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferablyfrom 4 to 5 silicon atoms. These are, for example,octamethylcyclotetrasiloxane sold in particular under the name VolatileSilicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia,decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158by Union Carbide, and Silbione® 70045 V5 by Rhodia, and mixturesthereof.

Mention may also be made of cyclocopolymers of thedimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ3109 sold by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes withorganic compounds derived from silicon, such as the mixture ofoctamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol(50/50) and the mixture of octamethylcyclotetrasiloxane andoxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 siliconatoms and having a viscosity of less than or equal to 5×10⁻⁶ m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under thename SH 200 by the company Toray Silicone. Silicones belonging to thiscategory are also described in the article published in Cosmetics andToiletries, Vol. 91, January 76, pp. 27-32, Todd & Byers, VolatileSilicone Fluids for Cosmetics.

Use is preferably made of non-volatile polydialkylsiloxanes,polydialkylsiloxane gums and resins, polyorganosiloxanes modified withthe organofunctional groups above, and mixtures thereof.

These silicones are more particularly chosen from polydialkylsiloxanes,among which mention may be made mainly of polydimethylsiloxanes havingtrimethylsilyl end groups. The viscosity of the silicones is measured at25° C. according to Standard ASTM 445 Appendix C.

Mention may be made, among these polydialkylsiloxanes, withoutlimitation, of the following commercial products:

-   -   the Silbione® oils of the 47 and 70 047 series or the Mirasil®        oils sold by Rhodia, for instance the 70 047 V 500 000 oil;    -   the oils of the Mirasil® series sold by the company Rhodia;    -   the oils of the 200 series from the company Dow Corning, such as        DC200 with a viscosity of 60 000 mm²/s;    -   the Viscasil® oils from General Electric and certain oils of the        SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes having dimethylsilanolend groups known under the name dimethiconol (CTFA), such as the oils ofthe 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made ofthe products sold under the names Abil Wax® 9800 and 9801 by the companyGoldschmidt, which are poly(C₁-C₂₀)dialkylsiloxanes.

The silicone gums that may be used in accordance with the invention arein particular polydialkylsiloxanes and preferably polydimethylsiloxaneswith high number-average molecular weights of between 200 000 and 1 000000, used alone or as a mixture in a solvent. This solvent may be chosenfrom volatile silicones, polydimethylsiloxane (PDMS) oils,polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes,methylene chloride, pentane, dodecane and tridecane, or mixturesthereof.

Products that may be used more particularly in accordance with theinvention are mixtures such as:

-   -   the mixtures formed from a polydimethylsiloxane hydroxylated at        the chain end, or dimethiconol (CTFA), and from a cyclic        polydimethylsiloxane, also known as cyclomethicone (CTFA), such        as the product Q2 1401 sold by the company Dow Corning;    -   the mixtures of a polydimethylsiloxane gum and of a cyclic        silicone, such as the product SF 1214 Silicone Fluid from the        company General Electric; this product is a gum SF 30        corresponding to a dimethicone, having a number-average        molecular weight of 500 000, dissolved in the oil SF 1202        Silicone Fluid corresponding to decamethylcyclopentasiloxane;    -   mixtures of two PDMSs with different viscosities, and more        particularly of a PDMS gum and a PDMS oil, such as the product        SF 1236 from the company General Electric. The product SF 1236        is a mixture of a gum SE 30 defined above with a viscosity of 20        m²/s and of an oil SF 96 with a viscosity of 5×10⁻⁶ m²/s. This        product preferably comprises 15% of gum SE 30 and 85% of an oil        SF 96.

The organopolysiloxane resins that may be used in accordance with theinvention are crosslinked siloxane systems containing the followingunits:R₂SiO_(2/2),R₃SiO_(1/2),RSiO_(3/2) and SiO_(4/2)

in which R represents an alkyl containing 1 to 16 carbon atoms. Amongthese products, those that are particularly preferred are those in whichR denotes a C₁-C₄ lower alkyl group, more particularly methyl.

Mention may be made, among these resins, of the product sold under thename Dow Corning 593 or those sold under the names Silicone Fluid SS4230 and SS 4267 by the company General Electric, which are silicones ofdimethyl/trimethylsiloxane structure.

Mention may also be made of the resins of the trimethylsiloxysilicatetype, sold in particular under the names X22-4914, X21-5034 and X21-5037by the company Shin-Etsu.

The organomodified silicones that may be used in accordance with theinvention are silicones as defined above and comprising in theirstructure one or more organofunctional groups as mentioned previously,attached via a hydrocarbon-based group.

Besides the silicones described above, the organomodified silicones maybe polydiarylsiloxanes, especially polydiphenylsiloxanes, andpolyalkylarylsiloxanes functionalized with the organofunctional groupsmentioned previously.

The polyalkylarylsiloxanes are chosen particularly from linear and/orbranched polydimethyl/methylphenylsiloxanes andpolydimethyl/diphenylsiloxanes with a viscosity of from 1×10⁻⁵ to 5×10⁻²m²/s at 25° C.

Among these polyalkylarylsiloxanes, examples that may be mentionedinclude the products sold under the following names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;    -   the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;    -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;    -   the silicones of the PK series from Bayer, such as the product        PK20;    -   the silicones of the PN and PH series from Bayer, such as the        products PN1000 and PH1000;    -   certain oils of the SF series from General Electric, such as SF        1023, SF 1154, SF 1250 and SF 1265.

Mention may be made, among the organomodified silicones, ofpolyorganosiloxanes comprising:

-   -   substituted or unsubstituted amino groups, such as the products        sold under the name GP 4 Silicone Fluid and GP 7100 by the        company Genesee or the products sold under the names Q2 8220 and        Dow Corning 929 or 939 by the company Dow Corning. The        substituted amino groups are, in particular, C₁-C₄ aminoalkyl        groups;    -   alkoxylated groups, such as the product sold under the name        Silicone Copolymer F-755 by SWS Silicones, and Abil Wax® 2428,        2434 and 2440 by the company Goldschmidt.

More particularly, the fatty substance(s) are chosen from compounds thatare liquid or pasty at room temperature (25° C.) and at atmosphericpressure.

Preferably, the fatty substance(s) are chosen from compounds that areliquid at a temperature of 25° C. and at atmospheric pressure.

The fatty substance(s) are advantageously chosen from hydrocarbons ofmore than 16 carbon atoms, C₆-C₁₆ alkanes, oils or triglycerides ofplant origin, liquid synthetic triglycerides, fatty alcohols, fatty acidand/or fatty alcohol esters other than triglycerides and non-siliconewaxes, non-silicone waxes and silicones, or mixtures thereof.

Preferably, the fatty substance is chosen from liquid petroleum jelly,C₆-C₁₆ alkanes, polydecenes, liquid fatty acid and/or fatty alcoholesters other than triglycerides, and liquid fatty alcohols, or mixturesthereof.

More preferentially, the fatty substance(s) are chosen from liquidpetroleum jelly, C₆-C₁₆ alkanes, polydecenes and liquid fatty alcoholssuch as 2-octyldodecanol.

The dye composition according to the invention comprises at least 15% byweight, preferably at least 20% by weight and even more particularly atleast 25% by weight of fatty substance, relative to the weight of thedye composition. According to a more particular embodiment, the totalamount of fatty substances is at least 30% by weight, particularly atleast 40% by weight and even more preferably at least 50% by weight,relative to the total weight of the dye composition.

Preferably, the fatty substance(s) are present in the dye compositionaccording to the invention in a content ranging from 15% to 80% byweight and more preferentially from 20% to 80% by weight relative to theweight of the dye composition. According to a more particularembodiment, the fatty substance content ranges from 25% to 80% byweight, preferably from 30% to 70% by weight and even moreadvantageously from 30% to 60% by weight relative to the weight of thedye composition. According to an even more preferably embodiment, thefatty substance content ranges from 40% to 60% by weight and even moreadvantageously from 50% to 60% by weight, relative to the weight of thedye composition.

Surfactants:

As indicated previously, the composition of the invention also comprisesone or more surfactants.

In particular, the surfactant(s) are chosen from anionic, amphoteric,zwitterionic, cationic and nonionic surfactants, and preferentiallynonionic surfactants.

The term “anionic surfactant” means a surfactant comprising, as ionic orionizable groups, only anionic groups. These anionic groups arepreferably chosen from the groups —C(O)OH, —C(O)O⁻, —SO₃H, —S(O)₂O⁻,—OS(O)₂OH, —OS(O)₂O⁻, —P(O)OH₂, —P(O)₂O⁻, —P(O)O₂ ⁻, —P(OH)₂, ═P(O)OH,—P(OH)O⁻, ═P(O)O⁻, ═POH and ═PO⁻, the anionic parts comprising acationic counterion such as those derived from an alkali metal, analkaline-earth metal, an amine or an ammonium.

As examples of anionic surfactants that may be used in the compositionaccording to the invention, mention may be made of alkyl sulfates, alkylether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates,monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates,alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates,alkyl sulfosuccinamates, acylisethionates and N-acyltaurates,polyglycoside polycarboxylic acid and alkyl monoester salts, acyllactylates, salts of D-galactoside uronic acids, salts of alkyl ethercarboxylic acids, salts of alkylaryl ether carboxylic acids, salts ofalkylamido ether carboxylic acids; and the corresponding non-salifiedforms of all these compounds; the alkyl and acyl groups of all thesecompounds comprising from 6 to 24 carbon atoms and the aryl groupdenoting a phenyl group.

These compounds can be oxyethylenated and then preferably comprise from1 to 50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylicacids can be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄alkyl polyglycoside-tartrates and C₆-C₂₄ alkyl polyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, it (they) may be chosenfrom alkali metal salts such as the sodium or potassium salt andpreferably the sodium salt, ammonium salts, amine salts and inparticular amino alcohol salts or alkaline-earth metal salts such as themagnesium salts.

Examples of amino alcohol salts that may especially be mentioned includemonoethanolamine, diethanolamine and triethanolamine salts,monoisopropanolamine, diisopropanolamine and triisopropanolamine salts,and 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol andtris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts, and in particular sodium ormagnesium salts, are preferably used.

Use is preferably made, among the anionic surfactants mentioned, of(C₆-C₂₄)alkyl sulfates, (C₆-C₂₄)alkyl ether sulfates comprising from 2to 50 ethylene oxide units, in particular in the form of alkali metal,ammonium, amino alcohol and alkaline-earth metal salts, or a mixture ofthese compounds.

In particular, it is preferable to use (C₁₂-C₂₀)alkyl sulfates,(C₁₂-C₂₀)alkyl ether sulfates comprising from 2 to 20 ethylene oxideunits, in particular in the form of alkali metal, ammonium, aminoalcohol and alkaline-earth metal salts, or a mixture of these compounds.Better still, it is preferable to use sodium lauryl ether sulfatecontaining 2.2 mol of ethylene oxide.

The amphoteric or zwitterionic surfactant(s), which are preferablynon-silicone surfactant(s), which may be used in the present inventionmay especially be derivatives of optionally quaternized secondary ortertiary aliphatic amines, in which derivatives the aliphatic group is alinear or branched chain comprising from 8 to 22 carbon atoms, saidamine derivatives containing at least one anionic group, for instance acarboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mentionmay be made in particular of (C₈-C₂₀)alkylbetaines, sulfobetaines,(C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines and(C₈-C₂₀)alkylamido(C₆-C₈)alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic aminederivatives that may be used, as defined above, mention may also be madeof the compounds of respective structures (A1) and (A2) below:R_(a)—C(O)—NH—CH₂—CH₂—N⁺(R_(b))(R_(c))—CH₂C(O)O—,M⁺,X⁻   (A1)

in which formula (A1):

-   -   R_(a) represents a C₁₀-C₃₀ alkyl or alkenyl group derived from        an acid R_(a)COOH preferably present in hydrolysed coconut oil,        or a heptyl, nonyl or undecyl group;    -   R_(b) represents a β-hydroxyethyl group; and    -   R_(c) represents a carboxymethyl group;    -   M⁺ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine, and    -   X⁻ represents an organic or mineral anionic counterion, such as        that chosen from halides, acetates, phosphates, nitrates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or (C₁-C₄)alkylaryl        sulfonates, in particular methyl sulfate and ethyl sulfate; or        alternatively M⁺ and X⁻ are absent;        R_(a)—C(O)—NH—CH₂—CH₂—N(B)(B′)  (A2)

in which formula (A2):

-   -   B represents the group —CH₂—CH₂—O—X′;    -   B′ represents the group —(CH₂)_(z)Y′, with z=1 or 2;    -   X′ represents the group —CH₂—C(O)OH, —CH₂—C(O)OZ′,        —CH₂—CH₂—C(O)OH, —CH₂—CH₂—C(O)OZ′, or a hydrogen atom;    -   Y′ represents the group —C(O)OH, —C(O)OZ′, —CH₂—CH(OH)—SO₃H or        the group —CH₂—CH(OH)—SO₃—Z′;    -   Z′ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine;    -   R_(a′) represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid        R_(a′)—C(O)OH preferably present in hydrolysed linseed oil or        coconut oil, an alkyl group, in particular of C₁₇ and its iso        form, or an unsaturated C₁₇ group.

These compounds are classified in the CTFA dictionary, 5th edition,1993, under the names disodium cocoamphodiacetate, disodiumlauroamphodiacetate, disodium caprylamphodiacetate, disodiumcapryloamphodiacetate, disodium cocoamphodipropionate, disodiumlauroamphodipropionate, disodium caprylamphodipropionate, disodiumcapryloamphodipropionate, lauroamphodipropionic acid andcocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold bythe company Rhodia under the trade name Miranol® C2M Concentrate.

Use may also be made of the compounds of formula (A3):R_(a)′—N(H)—CH(Y″)—(CH₂)_(n)—C(O)—N(H)—(CH₂)_(n′)—N(R_(d))(R_(e))  (A3)

in which formula (A3):

-   -   Y″ represents the group —C(O)OH, —C(O)OZ″, —CH₂—CH(OH)—SO₃H or        the group —CH₂—CH(OH)—SO₃—Z″;    -   R_(d) and R_(e) represent, independently of each other, a C₁-C₄        alkyl or hydroxyalkyl radical;    -   Z″ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine;    -   R_(a)″ represents a C₁₀-C₃₀ alkyl or alkenyl group derived from        an acid R_(a)″—C(O)OH preferably present in coconut oil or in        hydrolysed linseed oil;    -   n and n′ denote, independently of each other, an integer ranging        from 1 to 3.

Among the compounds of formula (A3), mention may be made of the compoundclassified in the CTFA dictionary under the name sodiumdiethylaminopropyl cocoaspartamide and sold by the company Chimex underthe name Chimexane HB.

Among the amphoteric or zwitterionic surfactants mentioned above, use ispreferably made of (C₈-C₂₀)alkylbetaines such as cocoylbetaine, and(C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines such as cocamidopropylbetaine,and mixtures thereof. More preferentially, the amphoteric orzwitterionic surfactant(s) are chosen from cocamidopropylbetaine andcocoylbetaine.

The cationic surfactant(s) that may be used in the composition accordingto the invention comprise, for example, optionally polyoxyalkylenatedprimary, secondary or tertiary fatty amine salts, quaternary ammoniumsalts, and mixtures thereof.

Examples of quaternary ammonium salts that may in particular bementioned include:

-   -   those corresponding to the general formula (A4) below:

in which formula (A4):

-   -   R₈ to R₁₁, which may be identical or different, represent a        linear or branched aliphatic group comprising from 1 to 30        carbon atoms, or an aromatic group such as aryl or alkylaryl, it        being understood that at least one of the groups R₈ to R₁₁        comprises from 8 to 30 carbon atoms and preferably from 12 to 24        carbon atoms; and    -   X⁻ represents an organic or mineral anionic counterion, such as        that chosen from halides, acetates, phosphates, nitrates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or (C₁-C₄)alkylaryl        sulfonates, in particular methyl sulfate and ethyl sulfate.

The aliphatic groups of R₈ to R₁₁ may also comprise heteroatomsespecially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic groups of R₈ to R₁₁ are chosen, for example, from C₁-C₃₀alkyl, C₁-C₃₀ alkoxy, polyoxy(C₂-C₆)alkylene, C₁-C₃₀ alkylamide,(C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂-C₂₂)alkyl acetate and C₁-C₃₀hydroxyalkyl groups, X⁻ is an anionic counterion chosen from halides,phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or(C₁-C₄)alkylaryl sulfonates.

Among the quaternary ammonium salts of formula (A4), preference is givenfirstly to tetraalkylammonium chlorides, for instancedialkyldimethylammonium or alkyltrimethylammonium chlorides in which thealkyl group contains approximately from 12 to 22 carbon atoms, inparticular behenyltrimethylammonium chloride, distearyldimethylammoniumchloride, cetyltrimethylammonium chloride, benzyldimethylstearylammoniumchloride, or else, secondly, distearoylethylhydroxyethylmethylammoniummethosulfate, dip almitoylethylhydroxyethylammonium methosulfate ordistearoylethylhydroxyethylammonium methosulfate, or else, lastly,palmitylamidopropyltrimethylammonium chloride orstearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold underthe name Ceraphyl® 70 by the company Van Dyk;

-   -   quaternary ammonium salts of imidazoline, for instance those of        formula (A5) below:

in which formula (A5):

-   -   R₁₂ represents an alkenyl or alkyl group comprising from 8 to 30        carbon atoms, for example fatty acid derivatives of tallow;    -   R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl group or an        alkenyl or alkyl group comprising from 8 to 30 carbon atoms;    -   R₁₄ represents a C₁-C₄ alkyl group;    -   R₁₅ represents a hydrogen atom or a C₁-C₄ alkyl group;    -   X⁻ represents an organic or mineral anionic counterion, such as        that chosen from halides, phosphates, acetates, lactates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or (C₁-C₄)alkylaryl        sulfonates.

R₁₂ and R₁₃ preferably denote a mixture of alkenyl or alkyl groupscontaining from 12 to 21 carbon atoms, for example fatty acidderivatives of tallow, R₁₄ denotes a methyl group, and R₁₅ denotes ahydrogen atom. Such a product is sold, for example, under the nameRewoquat® W 75 by the company Rewo;

-   -   quaternary diammonium or triammonium salts, particularly of        formula (A6) below:

in which formula (A6):

-   -   R₁₆ denotes an alkyl group comprising approximately from 16 to        30 carbon atoms, which is optionally hydroxylated and/or        interrupted with one or more oxygen atoms;    -   R₁₇ is chosen from hydrogen, an alkyl group comprising from 1 to        4 carbon atoms or a group —(CH₂)₃—N⁺(R_(16a))(R_(17a))(R_(18a)),        X;    -   R_(16a), R_(17a), R_(18a), R₁₈, R₁₉, R₂₀ and R₂₁, which may be        identical or different, are chosen from hydrogen and an alkyl        group comprising from 1 to 4 carbon atoms; and    -   X⁻, which may be identical or different, represent an organic or        mineral anionic counterion, such as that chosen from halides,        acetates, phosphates, nitrates, (C₁-C₄)alkyl sulfates,        (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates, particularly methyl        sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, sold by the companyFinetex (Quaternium 89), and Finquat CT, sold by the company Finetex(Quaternium 75);

-   -   quaternary ammonium salts containing one or more ester        functions, such as those of formula (A7) below:

in which formula (A7):

-   -   R₂₂ is chosen from C₁-C₆ alkyl groups and C₁-C₆ hydroxyalkyl or        C₁-C₆ dihydroxyalkyl groups;    -   R₂₃ is chosen from:        -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₂₂            hydrocarbon-based groups R₂₇,        -   a hydrogen atom,

    -   R₂₅ is chosen from        -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₆            hydrocarbon-based groups R₂₉,        -   a hydrogen atom,

    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are        chosen from linear or branched, saturated or unsaturated C₇-C₂₁        hydrocarbon-based groups;

    -   r, s and t, which may be identical or different, are integers        ranging from 2 to 6,

    -   r1 and t1, which may be identical or different, are equal to 0        or 1, with r2+r1=2r and t1+t2=2t,

    -   y is an integer ranging from 1 to 10,

    -   x and z, which may be identical or different, are integers        ranging from 0 to 10,

    -   X⁻ represents an organic or mineral anionic counterion,

with the proviso that the sum x+y+z is from 1 to 15, that when x is 0then R₂₃ denotes R₂₇, and that when z is 0 then R₂₅ denotes a linear orbranched, saturated or unsaturated C₁-C₆ hydrocarbon-based radical R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularlylinear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropylgroup, and more particularly a methyl or ethyl group.

Advantageously, the sum x+y+z is from 1 to 10.

When R₂₃ is an R₂₇ hydrocarbon-based group, it may be long and may havefrom 12 to 22 carbon atoms, or may be short and may have from 1 to 3carbon atoms.

When R₂₅ is an R₂₉ hydrocarbon-based group, it preferably has 1 to 3carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂₈, which may be identical or different,are chosen from linear or branched, saturated or unsaturated C₁₁-C₂₁hydrocarbon-based groups, and more particularly from linear or branched,saturated or unsaturated C₁₁-C₂₁ alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equalto 2 or 3, and even more particularly are equal to 2.

The anionic counterion X⁻ is preferably a halide, such as chloride,bromide or iodide; a (C₁-C₄)alkyl sulfate or a (C₁-C₄)alkyl- or(C₁-C₄)alkylaryl-sulfonate. However, it is possible to usemethanesulfonate, phosphate, nitrate, tosylate, an anion derived from anorganic acid, such as acetate or lactate, or any other anion that iscompatible with the ammonium comprising an ester function.

The anionic counterion X⁻ is even more particularly chloride, methylsulfate or ethyl sulfate.

Use is made more particularly, in the composition according to theinvention, of the ammonium salts of formula (A7) in which:

-   -   R₂₂ denotes a methyl or ethyl group,    -   x and y are equal to 1,    -   z is equal to 0 or 1,    -   r, s and t are equal to 2,    -   R₂₃ is chosen from:        -   the group

-   -   -   methyl, ethyl or C₁₄-C₂₂ hydrocarbon-based groups,        -   a hydrogen atom,

    -   R₂₅ is chosen from:        -   the group

-   -   -   a hydrogen atom,

    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are        chosen from linear or branched, saturated or unsaturated C₁₃-C₁₇        hydrocarbon-based groups, and preferably from linear or        branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl        groups.

Advantageously, the hydrocarbon radicals are linear.

Among the compounds of formula (A7), examples that may be mentionedinclude salts, especially the chloride or methyl sulfate, ofdiacyloxyethyldimethylammonium,diacyloxyethylhydroxyethylmethylammonium,monoacyloxyethyldihydroxyethylmethylammonium,triacyloxyethylmethylammonium ormonoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. Theacyl groups preferably contain from 14 to 18 carbon atoms and originatemore particularly from a plant oil, such as palm oil or sunflower oil.When the compound contains several acyl groups, these groups may beidentical or different.

These products are obtained, for example, by direct esterification oftriethanolamine, triisopropanolamine, an alkyldiethanolamine or analkyldiisopropanolamine, which are optionally oxyalkylenated, with fattyacids or with mixtures of fatty acids of vegetable or animal origin, orby transesterification of their methyl esters. This esterification isfollowed by a quaternization by means of an alkylating agent, such as analkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate,preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methylpara-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by thecompany Henkel, Stepanquat® by the company Stepan, Noxamium® by thecompany Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, amixture of quaternary ammonium salts of monoesters, diesters andtriesters with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least oneester function that are described in U.S. Pat. No. 4,874,554 and U.S.Pat. No. 4,137,180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride, soldby Kao under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester functioncontain two ester functions.

Among the cationic surfactants that may be present in the compositionaccording to the invention, it is more particularly preferred to choosecetyltrimethylammonium, behenyltrimethylammonium anddipalmitoylethyl-hydroxyethylmethylammonium salts, and mixtures thereof,and more particularly behenyltrimethylammonium chloride,cetyltrimethylammonium chloride and dipalmitoylethylhydroxyethylammoniummethosulfate, and mixtures thereof.

Examples of nonionic surfactants that may be used in the compositionused according to the invention are described, for example, in theHandbook of Surfactants by M. R. Porter, published by Blackie & Son(Glasgow and London), 1991, pp. 116-178.

Examples of oxyalkylenated nonionic surfactants that may be mentionedinclude:

-   -   oxyalkylenated (C₈-C₂₄)alkylphenols;    -   saturated or unsaturated, linear or branched, oxyalkylenated        C₈-C₃₀ alcohols;    -   saturated or unsaturated, linear or branched, oxyalkylenated        C₈-C₃₀ amides;    -   esters of saturated or unsaturated, linear or branched, C₈-C₃₀        acids and of polyethylene glycols;    -   polyoxyethylenated esters of saturated or unsaturated, linear or        branched, C₈-C₃₀ acids and of sorbitan;    -   fatty acid esters of sucrose;    -   (C₈-C₃₀)alkylpolyglycosides, (C₈-C₃₀)alkenylpolyglycosides,        which are optionally oxyalkylenated (0 to 10 oxyalkylene units)        and which comprise 1 to 15 glucose units, (C₈-C₃₀)alkylglucoside        esters;    -   saturated or unsaturated, oxyethylenated plant oils;    -   condensates of ethylene oxide and/or of propylene oxide, inter        alia, alone or as mixtures;    -   N—(C₈-C₃₀)alkylglucamine derivatives and        N—(C₈-C₃₀)acyl-methylglucamine derivatives;    -   aldobionamides;    -   amine oxides;    -   oxyethylenated and/or oxypropylenated silicones;

the surfactants contain a number of moles of ethylene oxide and/or ofpropylene oxide ranging advantageously from 1 to 100, more particularlyfrom 2 to 100, preferably from 2 to 50 and more advantageously from 2 to30. Advantageously, the nonionic surfactants do not compriseoxypropylene units.

In accordance with a preferred embodiment of the invention, theoxyalkylenated nonionic surfactants are chosen from oxyethylenatedC₈-C₃₀ alcohols comprising from 1 to 100 mol and more particularly from2 to 100 mol of ethylene oxide; polyoxyethylenated esters of saturatedor unsaturated, linear or branched C₈-C₃₀ acids and of sorbitancomprising from 1 to 100 and better still from 2 to 100 mol of ethyleneoxide.

As examples of monoglycerolated or polyglycerolated nonionicsurfactants, monoglycerolated or polyglycerolated C₈-C₄₀ alcohols arepreferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄₀ alcoholscorrespond to formula (A8) below:R₂₉O—[CH₂—CH(CH₂OH)—O]_(m)—H  (A8)

in which formula (A8):

-   -   —R₂₉ represents a linear or branched C₈-C₄₀ and preferably        C₈-C₃₀ alkyl or alkenyl radical; and    -   m represents a number ranging from 1 to 30 and preferably from 1        to 10.

As examples of compounds of formula (A8) that are suitable within thecontext of the invention, mention may be made of lauryl alcoholcontaining 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether),lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcoholcontaining 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether),cetearyl alcohol containing 2 mol of glycerol, cetearyl alcoholcontaining 6 mol of glycerol, oleocetyl alcohol containing 6 mol ofglycerol, and octadecanol containing 6 mol of glycerol.

The alcohol of formula (A8) may represent a mixture of alcohols in thesame way that the value of m represents a statistical value, which meansthat, in a commercial product, several species of polyglycerolated fattyalcohols may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is moreparticularly preferred to use the C₈/C₁₀ alcohol containing 1 mol ofglycerol, the C₁₀/C₁₂ alcohol containing 1 mol of glycerol and the C₁₂alcohol containing 1.5 mol of glycerol.

Preferably, the surfactant(s) are chosen from nonionic surfactants orfrom anionic surfactants. More particularly, the surfactant(s) presentin the composition are chosen from nonionic surfactants.

Preferentially, the nonionic surfactant used in the process of theinvention in the composition is a monooxyalkylenated orpolyoxyalkylenated, particularly monooxyethylenated orpolyoxyethylenated, or monooxypropylenated or polyoxypropylenated,nonionic surfactant, or a combination thereof, more particularlymonooxyethylenated or polyoxyethylenated, monoglycerolated orpolyglycerolated surfactants and alkylpolyglucosides.

Even more preferentially, the nonionic surfactants are chosen frompolyoxyethylenated sorbitan esters, polyoxyethylenated fatty alcoholsand alkylpolyglucosides, and mixtures thereof.

The surfactants may be present in the dye composition according to theinvention in a content ranging from 0.1% to 50% by weight and betterstill from 0.5% to 20% by weight relative to the total weight of thecomposition.

Oxidation Bases:

The composition of the invention comprises one or more oxidation baseschosen especially from heterocyclic bases and benzene bases, and theaddition salts and/or solvates thereof.

The benzene-based oxidation bases according to the invention areparticularly chosen from para-phenylenediamines,bis(phenyl)alkylenediamines, para-aminophenols and ortho-aminophenols,and the addition salts and/or solvates thereof.

Among the para-phenylenediamines that may be mentioned, for example, arepara-phenylenediamine, para-tolylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis((β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis((β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis((β-hydroxyethyl)amino-2-chloro aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotolueneand 3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition saltsand/or solvates thereof.

Among the para-phenylenediamines mentioned above, para-phenylenediamine,para-tolylenediamine, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition saltsand/or solvates thereof, are particularly preferred.

Among the bis(phenyl)alkylenediamines, examples that may be mentionedincludeN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition saltsand/or solvates thereof.

Among the para-aminophenols that may be mentioned, for example, arepara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts and/or solvates thereof.

Among the ortho-aminophenols, mention may be made, by way of example, of2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and5-acetamido-2-aminophenol, and the addition salts and/or solvatesthereof.

The heterocyclic bases according to the invention are more particularlychosen from pyridine derivatives, pyrimidine derivatives and pyrazolederivatives, and the addition salts and/or solvates thereof.

Among the pyridine derivatives, mention may be made of the compoundsdescribed, for example, in patents GB 1 026 978 and GB 1 153 196, suchas 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,3,4-diaminopyridine, and the addition salts and/or solvates thereof.

Other pyridine oxidation bases that are useful in the dyeing processaccording to the invention are the 3-aminopyrazolo[1,5-a]pyridineoxidation bases or the addition salts thereof described, for example, inpatent application FR 2 801 308. Examples that may be mentioned includepyrazolo[1,5-a]pyrid-3-ylamine,2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine,2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,2-methoxypyrazolo[1,5-a]pyrid-3-ylamine,(3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol,2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol,2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol,(3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol,3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine,pyrazolo[1,5-a]pyridine-3,7-diamine,7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,pyrazolo[1,5-a]pyridine-3,5-diamine,5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol,2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol and3-aminopyrazolo[1,5-a]pyridin-7-ol, and the addition salts and/orsolvates thereof.

Mention may be made, among pyrimidine derivatives, of the compoundsdescribed, for example, in patents DE 2359399, JP 88-169571, JP 05-63124and EP 0 770 375 or patent application WO 96/15765, such as2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine and the addition salts and/or solvates thereof,and the tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned are the compoundsdescribed in the patents DE 3843892, DE 4133957 and patent applicationsWO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the additionsalts and/or solvates thereof. Use may also be made of4,5-diamino-1-(β-methoxyethyl)pyrazole.

Use will preferably be made of a 4,5-diaminopyrazole and even morepreferentially of 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or anaddition salt and/or solvate thereof.

Pyrazole derivatives that may also be mentioned includediamino-N,N-dihydropyrazolopyrazolones and especially those described inpatent application FR-A-2 886 136, such as the following compounds andthe addition salts thereof:2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-oneor 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-oneand/or an addition salt and/or solvate thereof.

Use will preferably be made of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or anaddition salt and/or solvate thereof.

Heterocyclic bases that will preferentially be used include4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or anaddition salt and/or solvate thereof.

Preferably, the oxidation bases are chosen from para-phenylenediaminesand heterocyclic bases, and also addition salts and/or solvates thereof,and mixtures thereof.

The oxidation bases used in the composition according to the inventionmay advantageously represent from 0.0001% to 10% by weight relative tothe total weight of the composition, and preferably from 0.005% to 5% byweight relative to the total weight of the dye composition.

Couplers:

As indicated above, the dye composition according to the invention alsocomprises one or more meta-phenylenediamine-based couplers correspondingto formula (I), and also addition salts thereof, optical isomers,geometrical isomers and tautomers thereof and/or solvates thereof:

-   -   in which formula (I):        -   R₁ represents a linear or branched C₁-C₆ alkyl radical,            which may be substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHCOCH₃ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,        -   R₂ represents:        -    a hydrogen atom,        -    a linear or branched C₁-C₆ alkyl radical, which may be            substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,            -   C₁-C₆ alkoxy radicals,        -    a linear or branched C₁-C₆ alkoxy radical, which may be            substituted with one or more of the following:            -   —CONH₂ radicals,            -   —NHSO₂CH₃ radicals,            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   —COOH radicals,            -   C₁-C₆ alkoxy radicals,        -    a halogen radical,        -   R₃ and R₄ represent, independently of each other:        -    a hydrogen atom,        -    a linear or branched C₁-C₆ alkyl radical, which may be            substituted with one or more of the following:            -   di(C₁-C₆)alkylamino radicals,            -   hydroxyl radicals,            -   amino radicals,            -   C₁-C₆ alkoxy radicals,        -   X represents an oxygen or sulfur atom,    -   n represents an integer ranging from 0 to 2.

According to one embodiment, R₁ represents a linear C₁-C₄ and especiallyC₁ alkyl radical, optionally substituted with one or more hydroxylgroups, an amino group or a group —NHCOCH₃.

Preferably, R₁ represents an unsubstituted linear C₁-C₄ and especiallyC₁ alkyl radical.

According to one embodiment, R₃ and R₄ represent, independently of eachother, a hydrogen atom or a linear C₁-C₆, in particular C₁-C₄ and moreparticularly C₂ alkyl radical, optionally substituted with a hydroxylgroup.

Preferably, R₃ represents a hydrogen atom and R₄ represents a hydrogenatom or a linear C₁-C₆, in particular C₁-C₄ and especially C₂ alkylradical, optionally substituted with a hydroxyl group.

More preferentially, R₃ and R₄ represent a hydrogen atom.

According to one embodiment, R₂ represents a hydrogen atom, a linearC₁-C₄ and especially C₁ alkyl radical or a linear C₁-C₄ alkoxy radicaloptionally substituted with a hydroxyl group.

In accordance with one embodiment, X represents an oxygen atom.

According to this embodiment, R₃ and R₄ preferentially represent,independently of each other, a hydrogen atom or a linear C₁-C₆, inparticular C₁-C₄ and more particularly C₂ alkyl radical, optionallysubstituted with a hydroxyl group.

In particular, R₃ and R₄ preferentially represent, in accordance withthis embodiment, a hydrogen atom.

In accordance with this embodiment, R₂ represents a hydrogen atom, alinear C₁-C₄ and especially C₁ alkyl radical, or a linear C₁-C₄ alkoxyradical optionally substituted with a hydroxyl group, and R₃ and R₄represent, independently of each other, a hydrogen atom or a linearC₁-C₆, in particular C₁-C₄ and more particularly C₂ alkyl radical,optionally substituted with a hydroxyl group.

According to another embodiment, X represents a sulfur atom.

In accordance with this embodiment, R₃ and R₄ preferentially represent ahydrogen atom.

According to this embodiment, R₃ and R₄ preferentially represent ahydrogen atom and R₁ represents a linear C₁-C₄ and especially C₁ alkylradical, optionally substituted with one or more hydroxyl groups, anamino group or a group —NHCOCH₃.

Preferably, the meta-phenylenediamine-based coupler(s) corresponding toformula (I) are chosen from the following compounds, and also theaddition salts thereof, optical isomers, geometrical isomers andtautomers thereof, and/or solvates thereof:

More preferentially, the couplers used according to the presentinvention are chosen from couplers (1) and (2), and also the additionsalts thereof, optical isomers, geometrical isomers and tautomersthereof, and/or solvates thereof.

According to one embodiment, the dye composition according to theinvention comprises:

-   -   (i) one or more fatty substances,    -   (ii) one or more surfactants,    -   (iii) one or more oxidation bases chosen from        para-phenylenediamines and heterocyclic bases, and also addition        salts and/or solvates thereof, and mixtures thereof,    -   (iv) one or more basifying agents,    -   (v) one or more couplers corresponding to formula (I) chosen        from couplers (1) and (2), and also the addition salts thereof,        optical isomers, geometrical isomers and tautomers thereof,        and/or solvates thereof,    -   (vi) one or more chemical oxidizing agents,

the fatty substance content representing in total at least 15% by weightrelative to the total weight of the said dye composition.

The meta-phenylenediamine-based coupler(s) of formula (I) may be presentin the dye composition according to the invention in a content rangingfrom 0.0001% to 10% by weight and preferably from 0.005% to 5% by weightrelative to the total weight of the dye composition.

Basifying Agents:

As indicated previously, the dye composition according to the inventionalso comprises one or more basifying agents.

The basifying agent(s) may be mineral or organic or hybrid.

The mineral basifying agent(s) are preferably chosen from aqueousammonia, alkali metal carbonates or bicarbonates such as sodiumcarbonate, potassium carbonate, sodium bicarbonate or potassiumbicarbonate, sodium hydroxide or potassium hydroxide, or mixturesthereof.

The organic basifying agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6. It should be noted that it is thepK_(b) corresponding to the function of highest basicity. In addition,the organic amines do not comprise an alkyl or alkenyl fatty chaincomprising more than ten carbon atoms.

The organic basifying agent(s) are chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds of formula (II) below:

in which formula (II) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,and/or optionally interrupted with one or more heteroatoms such as O, orNR_(u), R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identical ordifferent, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of amines of formula (II) that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” means an organic amine comprising a primary,secondary or tertiary amine function, and one or more linear or branchedC₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

The organic amines chosen from alkanolamines such as monoalkanolamines,dialkanolamines or trialkanolamines, comprising one to three identicalor different C₁-C₄ hydroxyalkyl radicals are in particular suitable forcarrying out the invention.

Among compounds of this type, mention may be made of monoethanolamine(MEA), diethanolamine, triethanolamine, mono isopropanolamine,diisopropanolamine, N-dimethylaminoethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that may be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function chosen more particularly from carboxylic acid,sulfonic acid, phosphonic acid or phosphoric acid functions. The aminoacids may be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may bemade especially of aspartic acid, glutamic acid, alanine, arginine,ornithine, citrulline, asparagine, carnitine, cysteine, glutamine,glycine, histidine, lysine, isoleucine, leucine, methionine,N-phenylalanine, proline, serine, taurine, threonine, tryptophan,tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising anadditional amine function optionally included in a ring or in a ureidofunction.

Such basic amino acids are preferably chosen from those corresponding toformula (III) below, and also salts thereof:

in which formula (III), R represents a group chosen from:

The compounds corresponding to formula (III) are histidine, lysine,arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may in particular be made of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. Asamino acid dipeptides that may be used in the present invention, mentionmay in particular be made of carnosine, anserine and balenine.

The organic amine may also be chosen from compounds comprising aguanidine function. As amines of this type that may be used in thepresent invention, besides arginine, which has already been mentioned asan amino acid, mention may be made especially of creatine, creatinine,1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin,agmatine, N-amidino alanine, 3-guanidinopropionic acid,4-guanidinobutyric acid and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Hybrid compounds that may be mentioned include the salts of the aminesmentioned previously with acids such as carbonic acid or hydrochloricacid.

Use may in particular be made of guanidine carbonate or monoethanolaminehydrochloride.

Preferably, the basifying agent(s) present in the composition of theinvention are chosen from alkanolamines, amino acids in neutral or ionicform, in particular basic amino acids, and preferably corresponding tothose of the formula (III). Even more preferentially, the basifyingagent(s) are chosen from monoethanolamine (MEA) and basic amino acids inneutral or ionic form.

Advantageously, the composition according to the invention has a contentof basifying agent(s) ranging from 0.01% to 30% by weight and preferablyfrom 0.1% to 20% by weight relative to the weight of the composition.

According to a first particular embodiment, the composition according tothe invention, or the process according to the invention, does not useaqueous ammonia, or a salt thereof, as basifying agent.

According to a second embodiment, if the composition or the processaccording to the invention were to use aqueous ammonia, or a saltthereof, as basifying agent, its content advantageously would not exceed0.03% by weight (expressed as NH₃) and preferably would not exceed 0.01%by weight, relative to the weight of the composition of the invention.

Preferably, if the composition comprises aqueous ammonia, or a saltthereof, then the weight amount of basifying agent(s) other than theaqueous ammonia is greater than that of the aqueous ammonia (expressedas NH₃).

Chemical Oxidizing Agent:

The dye composition of the invention also comprises one or more chemicaloxidizing agents.

The term “chemical oxidizing agent” means an oxidizing agent other thanatmospheric oxygen. More particularly, the chemical oxidizing agent(s)are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates,peroxygenated salts, for instance persulfates, perborates, peracids andprecursors thereof and percarbonates of alkali metals or alkaline-earthmetals.

This oxidizing agent advantageously consists of hydrogen peroxideespecially as an aqueous solution (aqueous hydrogen peroxide solution),the concentration of which may range more particularly from 0.1% to 50%by weight, even more preferentially from 0.5% to 20% by weight andbetter still from 1% to 15% by weight, relative to the weight of thecomposition.

Preferably, the composition of the invention does not contain anyperoxygenated salts.

Additional Couplers

The dye composition according to the present invention may also containone or more additional couplers other than themeta-phenylenediamine-based couplers of formula (I) as describedpreviously.

Among these additional couplers, mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers and heterocyclic couplers, and also theaddition salts thereof and/or solvates thereof.

Examples that may be mentioned include 1,3-dihydroxybenzene,1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline,3-ureido-1-(dimethylamino)benzene, sesamol,1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine,6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline,2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b][1,2,4]triazole,2,6-dimethyl[3,2-c][1,2,4]triazole and6-methylpyrazolo[1,5-a]benzimidazole, and mixtures thereof.

The additional coupler(s) each advantageously represent from 0.0001% to10% by weight, relative to the total weight of the composition, andpreferably from 0.005% to 5% by weight, relative to the total weight ofthe composition of the invention.

Additional Dyes

The dye composition according to the present invention may also containone or more direct dyes.

The latter are more particularly chosen from ionic or nonionic species,preferably cationic or nonionic species. These direct dyes may besynthetic or of natural origin.

Examples of suitable direct dyes that may be mentioned include azodirect dyes; methine direct dyes; carbonyl direct dyes; azine directdyes; nitro(hetero)aryl direct dyes; tri(hetero)arylmethane direct dyes;porphyrin direct dyes; phthalocyanine direct dyes, and natural directdyes, alone or as mixtures.

More particularly, the azo dyes comprise an —N═N— function, the twonitrogen atoms of which do not simultaneously participate in a ring.However, it is not excluded for one of the two nitrogen atoms of thesequence —N═N— to be a engaged in a ring.

The dyes of the methine family are more particularly compoundscomprising at least one sequence chosen from >C═C< and —N═C< in whichthe two atoms do not simultaneously participate in a ring. However, itis pointed out that one of the nitrogen or carbon atoms of the sequencesmay be engaged in a ring. More particularly, the dyes of this family arederived from compounds of the type such as methines, azomethines,monoarylmethanes and diarylmethanes, indoamines (or diphenylamines),indophenols, indoanilines, carbocyanines, azacarbocyanines and isomersthereof, diazacarbocyanines and isomers thereof, tetraazacarbocyaninesand hemicyanines.

As regards the dyes of the carbonyl family, examples that may bementioned include dyes chosen from acridone, benzoquinone,anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone,pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone,(iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone,anthrapyridone, pyrazoloquinazolone, perinone, quinacridone,quinophthalone, indigoid, thio indigo, naphthalimide, anthrapyrimidine,diketopyrrolopyrrole and coumarin.

As regards the dyes of the cyclic azine family, mention may be madeespecially of azine, xanthene, thioxanthene, fluorindine, acridine,(di)oxazine, (di)thiazine and pyronin.

The nitro(hetero)aromatic dyes are more particularly nitrobenzene ornitropyridine direct dyes.

As regards the dyes of porphyrin or phthalocyanine type, it is possibleto use cationic or non-cationic compounds, optionally comprising one ormore metals or metal ions, for instance alkali metals, alkaline-earthmetals, zinc and silicon.

Examples of particularly suitable direct dyes that may be mentionedinclude nitrobenzene dyes; azo direct dyes; azomethine direct dyes;methine direct dyes; azacarbocyanine direct dyes, for instancetetraazacarbocyanines (tetraazapentamethines); quinone and in particularanthraquinone, naphthoquinone or benzoquinone direct dyes; azine directdyes; xanthene direct dyes; triarylmethane direct dyes; indoamine directdyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin directdyes and natural direct dyes, alone or as mixtures.

Among the natural direct dyes that may be used according to theinvention, mention may be made of lawsone, juglone, alizarin, purpurin,carminic acid, kermesic acid, purpurogallin, protocatechaldehyde,indigo, isatin, curcumin, spinulo sin, apigenidin and orceins. Use mayalso be made of extracts or decoctions comprising these natural dyes andin particular henna-based poultices or extracts.

When they are present, the direct dye(s) more particularly representfrom 0.0001% to 10% by weight and preferably from 0.005% to 5% by weightrelative to the total weight of the composition.

Solvent:

The dye composition may also comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include linear orbranched C₂-C₄ alkanols, such as ethanol and isopropanol; glycerol;polyols and polyol ethers, for instance 2-butoxyethanol, propyleneglycol, dipropylene glycol, propylene glycol monomethyl ether,diethylene glycol monomethyl ether and monoethyl ether, and alsoaromatic alcohols or ethers, for instance benzyl alcohol orphenoxyethanol, and mixtures thereof.

The organic solvent(s), if they are present, represent a content usuallyranging from 1% to 40% by weight and preferably from 5% to 30% by weightrelative to the weight of the composition.

Other Additives:

The composition according to the invention may also contain variousadjuvants conventionally used in hair dye compositions, such as anionic,cationic, nonionic, amphoteric or zwitterionic polymers or mixturesthereof; mineral thickeners, and in particular fillers such as clays ortalc; organic thickeners with, in particular, anionic, cationic,nonionic and amphoteric polymeric associative thickeners; antioxidants;penetrants; sequestrants; fragrances; dispersants; film-forming agents;ceramides; preserving agents; opacifiers.

The above adjuvants are generally present in an amount, for each ofthem, of between 0.01% and 20% by weight relative to the weight of thecomposition.

The composition may especially comprise one or more mineral thickenerschosen from organophilic clays and fumed silicas, or mixtures thereof.

The organophilic clay may be chosen from montmorillonite, bentonite,hectorite, attapulgite and sepiolite, and mixtures thereof. The clay ispreferably a bentonite or a hectorite.

These clays may be modified with a chemical compound chosen fromquaternary amines, tertiary amines, amine acetates, imidazolines, aminesoaps, fatty sulfates, alkylarylsulfonates and amine oxides, andmixtures thereof.

Mention may be made, as organophilic clays, of quaternium-18 bentonites,such as those sold under the names Bentone 3, Bentone 38 and Bentone 38Vby the company Rheox, Tixogel VP by the company United Catalyst andClaytone 34, Claytone 40 and Claytone XL by the company Southern Clay;stearalkonium bentonites, such as those sold under the names Bentone 27by the company Rheox, Tixogel LG by the company United Catalyst andClaytone AF and Claytone APA by the company Southern Clay; andquaternium-18/benzalkonium bentonite, such as those sold under the namesClaytone HT and Claytone PS by the company Southern Clay.

The fumed silicas may be obtained by high-temperature hydrolysis of avolatile silicon compound in an oxyhydrogen flame, producing a finelydivided silica. This process makes it possible especially to obtainhydrophilic silicas bearing a large number of silanol groups at theirsurface. Such hydrophilic silicas are sold, for example, under the namesAerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380®by the company Degussa and Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-SilLM-130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by the company Cabot.

It is possible to chemically modify the surface of the silica bychemical reaction for the purpose of reducing the number of silanolgroups. It is especially possible to replace silanol groups withhydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be:

-   -   trimethylsiloxyl groups, which are obtained in particular by        treating fumed silica in the presence of hexamethyldisilazane.        Silicas thus treated are known as “Silica silylate” according to        the CTFA (6th Edition, 1995). They are sold, for example, under        the references Aerosil R812® by the company Degussa and        Cab-O-Sil TS-530® by the company Cabot,    -   dimethylsilyloxyl or polydimethylsiloxane groups, which are        obtained in particular by treating fumed silica in the presence        of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus        treated are known as “Silica dimethyl silylate” according to the        CTFA (6th edition, 1995). They are sold, for example, under the        references Aerosil R972® and Aerosil R974® by the company        Degussa and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the        company Cabot.

The fumed silica preferably has a particle size that may be nanometricto micrometric, for example ranging from about 5 to 200 nm.

Preferably, the composition comprises a hectorite, an organomodifiedbentonite or an optionally modified fumed silica.

When it is present, the mineral thickener represents from 1% to 30% byweight relative to the weight of the composition.

The composition may also comprise one or more organic thickeners.

These thickeners may be chosen from fatty acid amides (coconut aciddiethanolamide or monoethanolamide, oxyethylenated alkyl ethercarboxylic acid monoethanolamide), polymeric thickeners, such ascellulose-based thickeners (hydroxyethylcellulose,hydroxypropylcellulose, carboxymethylcellulose), guar gum andderivatives thereof (hydroxypropyl guar), gums of microbial origin(xanthan gum, scleroglucan gum), crosslinked homopolymers of acrylicacid or of acrylamidopropanesulfonic acid and associative polymers(polymers comprising hydrophilic regions and hydrophobic regions havinga fatty chain (alkyl or alkenyl chain comprising at least 10 carbonatoms) which are capable, in an aqueous medium, of reversiblyassociating with each other or with other molecules).

According to a specific embodiment, the organic thickener is chosen fromcellulose-based thickeners (hydroxyethylcellulose,hydroxypropylcellulose, carboxymethylcellulose), guar gum andderivatives thereof (hydroxypropyl guar), gums of microbial origin(xanthan gum, scleroglucan gum) and crosslinked homopolymers of acrylicacid or of acrylamidopropanesulfonic acid, and preferably fromcellulose-based thickeners with in particular hydroxyethylcellulose.

The content of organic thickener(s), if they are present, usually rangesfrom 0.01% to 20% by weight and preferably from 0.1% to 5% by weight,relative to the weight of the composition.

The composition of the invention can be provided in various forms, forinstance a solution, an emulsion (milk or cream) or a gel.

According to a preferred embodiment, the dye composition according tothe invention comprises:

(i) one or more non-silicone fatty substances which are liquid at atemperature of 25° C. and at atmospheric pressure, and which do notcontain any C₂-C₃ (poly)oxyalkylene units or any (poly)glycerol units,

(ii) one or more surfactants chosen from nonionic surfactants,

(iii) one or more oxidation bases chosen especially from heterocyclicbases and benzene-based bases, and addition salts thereof and/orsolvates thereof,

(iv) one or more basifying agents chosen from alkanolamines and aminoacids in neutral or ionic form, or mixtures thereof,

(v) one or more meta-phenylenediamine-based couplers of formula (I) asdescribed previously,

(vi) one or more chemical oxidizing agents,

the fatty substance content representing in total at least 15% byweight, advantageously at least 20% by weight and preferably at least25% by weight of fatty substance, relative to the total weight of thesaid dye composition. According to a more particular embodiment, thefatty substance content represents in total at least 30% by weight,particularly at least 40% by weight and even more preferably at least50% by weight, relative to the total weight of the said dye composition.

Preferably, the dye composition according to the present inventioncomprises:

(i) one or more non-silicone fatty substances, which are liquid at atemperature of 25° C. and at atmospheric pressure, and which do notcontain any C₂-C₃ (poly)oxyalkylene units or any (poly)glycerol units,chosen from liquid petroleum jelly, liquid esters of fatty acids and/orof fatty alcohols other than triglycerides, and liquid fatty alcohols,or mixtures thereof,

(ii) one or more surfactants chosen from nonionic surfactants,

(iii) one or more oxidation bases chosen from heterocyclic bases,para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenolsand ortho-aminophenols, and addition salts thereof and/or solvatesthereof,

(iv) one or more basifying agents chosen from alkanolamines and basicamino acids of formula (III), or mixtures thereof,

(v) one or more meta-phenylenediamine-based couplers of formula (I) asdescribed previously, in which:

-   -   X represents an oxygen atom,    -   R₁ represents a linear C₁-C₄ and especially C₁ alkyl radical,        optionally substituted with one or more hydroxyl groups, an        amino group or a group —NHCOCH₃,    -   R₃ and R₄ represent, independently of each other, a hydrogen        atom or a linear C₁-C₆, in particular C₁-C₄ and more        particularly C₂ alkyl radical, optionally substituted with a        hydroxyl group,    -   R₂ represents a hydrogen atom, a linear C₁-C₄ and especially C₁        alkyl radical or a linear C₁-C₄ alkoxy radical optionally        substituted with a hydroxyl group,    -   n is an integer ranging from 0 to 2,

(vi) one or more chemical oxidizing agents,

the fatty substance content representing in total at least 15% byweight, advantageously at least 20% by weight and preferably at least25% by weight of fatty substance, relative to the total weight of thesaid dye composition, and, in accordance with a more particularembodiment, the fatty substance content is not more than 80% by weight,and preferably the said content ranges from 30% to 70% by weight andmore advantageously from 30% to 60% by weight relative to the weight ofthe dye composition. According to a more preferably embodiment, thefatty substance content represents in total at least 30% by weight,particularly at least 40% by weight and even more preferably at least50% by weight, relative to the total weight of the said dye compositionand preferably the said content ranges from 40% to 60% by weight andadvantageously from 50% to 60% by weight, relative to the weight of thedye composition.

More preferentially, the dye composition according to the presentinvention comprises:

(i) one or more non-silicone fatty substances, which are liquid at atemperature of 25° C. and at atmospheric pressure, and which do notcontain any C₂-C₃ (poly)oxyalkylene units or any (poly)glycerol units,chosen from liquid petroleum jelly, liquid esters of fatty acids and/orof fatty alcohols, and liquid fatty alcohols, or mixtures thereof,

(ii) one or more surfactants chosen from nonionic surfactants chosenfrom monooxyalkylene and polyoxyalkylene, especially polyoxyethylene,nonionic surfactants, and optionally oxyethylenated alkylpolyglucosides,

(iii) one or more oxidation bases chosen from heterocyclic bases,para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenolsand ortho-aminophenols, and addition salts thereof and/or solvatesthereof,

(iv) one or more basifying agents chosen from alkanolamines, inparticular monoethanolamine, and basic amino acids of formula (III), ormixtures thereof,

(v) one or more meta-phenylenediamine-based couplers of formula (I)chosen from couplers (1) and (2), and also the addition salts thereof,optical isomers, geometrical isomers and tautomers thereof, and/orsolvates thereof,

(vi) hydrogen peroxide as chemical oxidizing agent, especially anaqueous hydrogen peroxide solution,

the fatty substance content representing in total at least 15% byweight, advantageously at least 20% by weight and preferably at least25% by weight of fatty substance, relative to the total weight of thesaid dye composition, and, in accordance with a more particularembodiment, the fatty substance content is not more than 80% by weight,and preferably the said content ranges from 30% to 70% by weight andmore advantageously from 30% to 60% by weight relative to the weight ofthe dye composition. According to a more preferably embodiment, thefatty substance content represents in total at least 30% by weight,particularly at least 40% by weight and even more preferably at least50% by weight, relative to the total weight of the said dye compositionand preferably the said content ranges from 40% to 60% by weight andadvantageously from 50% to 60% by weight, relative to the weight of thedye composition.

PROCESSES OF THE INVENTION

The process for dyeing keratin fibres, in particular human keratinfibres such as the hair, consists in applying to the said fibres acomposition as defined previously.

In particular, the dye composition used in the process according to theinvention is applied to wet or dry keratin fibres.

It is usually left in place on the fibres for a time generally of from 1minute to 1 hour and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process conventionally ranges fromroom temperature (from 15° C. to 25° C.) to 80° C. and preferably fromroom temperature to 60° C.

After the treatment, the human keratin fibres are advantageously rinsedwith water. They may optionally be washed with a shampoo, followed byrinsing with water, before being dried or left to dry.

The composition applied in the process according to the invention isgenerally prepared via extemporaneous mixing of at least twocompositions, preferably two or three compositions.

In a first variant of the invention, the composition applied in theprocess according to the invention is derived from the extemporaneousmixing of two compositions.

In particular, a composition (A) (free of chemical oxidizing agent)comprising one or more oxidation bases, one or moremeta-phenylenediamine-based couplers of formula (I) and one or morebasifying agents is mixed with a composition (B) comprising one or morechemical oxidizing agents; at least one of the compositions (A) and (B)comprising one or more fatty substances and one or more surfactants, thefatty substance content of the composition according to the invention,resulting from the mixing of compositions (A) and (B) comprising atleast 15% by weight of fatty substance.

At least one of the compositions (A) and (B) is advantageously aqueous.

The term “aqueous composition” means a composition comprising at least5% by weight of water, relative to the weight of this composition.

Preferably, an aqueous composition comprises more than 10% by weight ofwater and even more advantageously more than 20% by weight of water.

Preferably, composition (A) is aqueous. Preferably, composition (B) isalso aqueous.

In this variant, composition (A) preferably comprises at least 30% andbetter still at least 50% by weight of fatty substances and even moreadvantageously at least 30% and more particularly at least 50% by weightof fatty substances that are liquid at room temperature (25° C.),relative to the weight of this composition (A).

Preferably, composition (A) is a direct emulsion (oil-in-water: 0/W) oran inverse emulsion (water-in-oil: W/0), and preferably a directemulsion (0/W).

In this variant, compositions (A) and (B) are preferably mixed in an(A)/(B) weight ratio ranging from 0.2 to 10 and better still from 0.5 to2.

In accordance with this first variant, the dyeing process according tothe invention consists, in a first stage, in mixing composition (A) andcomposition (B) as defined previously just before application to thekeratin fibres, and, in a second stage, in applying to the said keratinfibres the composition resulting from the mixing of compositions (A) and(B).

In a second variant of the invention, the composition used in theprocess according to the invention results from the extemporaneousmixing of three compositions. In particular, the three compositions areaqueous or alternatively at least one of them is anhydrous.

More particularly, within the meaning of the invention, the term“anhydrous cosmetic composition” means a cosmetic composition having awater content of less than 5% by weight, preferably of less than 2% byweight and even more preferably of less than 1% by weight, relative tothe weight of the said composition. It should be noted that the waterpresent in the composition is more particularly “bound water”, such asthe water of crystallization of the salts or traces of water absorbed bythe raw materials used in the preparation of the compositions accordingto the invention.

Preferably, use is made of two aqueous compositions (B′) and (C′) andone anhydrous composition (A′).

The anhydrous composition (A′) (free of chemical oxidizing agent) thenpreferably comprises one or more fatty substances, and morepreferentially one or more fatty substances that are liquid at roomtemperature and atmospheric pressure.

Composition (B′) (free of chemical oxidizing agent) then preferablycomprises one or more oxidation bases and one or moremeta-phenylenediamine-based couplers of formula (I).

Composition (C′) then preferably comprises one or more chemicaloxidizing agents.

According to this preferred mode of the second variant, the basifyingagent(s) are included in the compositions (A′) and/or (B′) andpreferably only in composition (B′). As regards the surfactant(s), theyare included in at least one of the compositions (A′), (B′) and (C′).

According to this preferred mode, the composition according to theinvention, i.e. resulting from the extemporaneous mixing of the threecompositions (A′), (B′) and (C′), has a fatty substance content of atleast 15% by weight, preferably at least 20% by weight and even moreadvantageously at least 25% by weight of fatty substance, relative tothe weight of the composition resulting from mixing the threeabovementioned compositions. According to a more preferably embodiment,the extemporaneous mixing of the three compositions (A′), (B′) and (C′)has a fatty substance content of at least 30% by weight, particularly atleast 40% by weight and even more preferably at least 50% by weight offatty substance, relative to the weight of the composition resultingfrom mixing the three abovementioned compositions.

In this variant, compositions (A′), (B′) and (C′) are preferably mixedtogether in a weight ratio [(A′)+(B′)]/(C′) ranging from 0.2 to 10 andmore particularly from 0.5 to 2 and in a weight ratio (A′)/(B′) rangingfrom 0.5 to 10 and preferably from 1 to 5.

In accordance with this second variant, the dyeing process according tothe invention consists, in a first step, in mixing compositions (A′),(B′) and (C′) as defined previously just before application to thekeratin fibres, and, in a second step, in applying to the said keratinfibres the composition resulting from the mixing of compositions (A′),(B′) and (C′).

Devices:

The invention relates to a first multi-compartment device comprising afirst compartment containing composition (A) as described above and atleast a second compartment containing composition (B) as describedabove; the compositions (A) and (B) of the compartments being intendedto be mixed together before application to give a composition accordingto the invention; the amount of fatty substance of which represents atleast 15% by weight, preferably at least 20% by weight and even moreadvantageously at least 25% by weight relative to the weight of theformulation resulting from the mixing of compositions (A) and (B).According to a preferably embodiment the amount of fatty substancerepresents at least 30% by weight, more particularly 40% by weight andeven more advantageously at least 50% by weight relative to the weightof the formulation resulting from the mixing of compositions (A) and(B).

The invention also relates to a second multi-compartment devicecomprising a first compartment containing composition (A′) as describedabove and a second compartment containing a cosmetic composition (B′) asdescribed above and at least a third compartment comprising composition(C′) as described above, the compositions of the compartments beingintended to be mixed together before application to give the compositionaccording to the invention; the amount of fatty substance in thecomposition representing at least 15% by weight, preferably at least 20%by weight and even more advantageously at least 25% by weight relativeto the weight of the composition according to the invention, i.e.resulting from the mixing of compositions (A′), (B′) and (C′). Accordingto a preferably embodiment the amount of fatty substance represents atleast 30% by weight, more particularly 40% by weight and even moreadvantageously at least 50% by weigh relative to the weight of thecomposition according to the invention, i.e. resulting from the mixingof compositions (A′), (B′) and (C′).

The present invention also relates to the use of the dye composition asdefined previously for dyeing keratin fibres, in particular humankeratin fibres such as the hair.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

EXAMPLES I. Protocol

Compositions (A) and (B) below are prepared from the ingredientsindicated in the table below. The amounts mentioned are indicated ingrams of active material.

Composition (A)

Composition A 2-Octyldodecanol 11.5 g Liquid petroleum jelly 75.5 gOxyethylenated lauryl alcohol (2 OE) 3 g Oxyethylenated sorbitanmonolaurate (4 OE) 11 g

Composition (B)

Composition B Monoethanolamine 15.05 g Sodium metabisulfite 0.7 gAscorbic acid 0.25 g Diethylenetriaminepentaacetic acid 1 g Propyleneglycol 6.2 g 96% ethanol 8.8 g Hexylene glycol 3 g Dipropylene glycol 3g Oxidation base 1.45 × 10⁻² mol Coupler 1.45 × 10⁻² mol Water qs 100 g

Procedure

At the time of use, 0.828 ml of composition (A), 0.33 ml of composition(B) and 1.242 ml of a composition (C) of 20-volumes aqueous hydrogenperoxide solution are mixed together.

The mixture obtained is applied to 200 mg of locks of natural haircontaining 90% white hairs. After a leave-on time of 30 minutes at roomtemperature, the locks are rinsed and then washed with a standardshampoo.

II. Calculation of the Colour Variation (ΔE_(ab)*)

The coloration build-up (ΔE_(ab)*) was evaluated in the CIE L* a* b*system. In this L* a* b* system, L* represents the intensity of thecolour, a* indicates the green/red colour axis and b* indicates theblue/yellow colour axis. The lower the value of L*, the darker or moreintense the colour.

The value of ΔE_(ab)* was calculated from the values of L* a* b*according to equation (i) below:ΔE _(ab)*=√{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²(b*−b_(o)*)²)}  (i)

The coloration build-up (ΔE_(Lab)*) was calculated on the locks ofuntreated hair (L₀*, a₀* and b₀*) and on locks of dyed hair (L*, a* andb*). The values of L₀*, a₀* and b₀* for the untreated natural whitehairs are, respectively, 55.56, 2.06 and 12.29.

The greater the value of ΔE_(ab)*, the better the coverage of thefibres.

IV. Results

Coupler Base L a b ΔE_(ab)*

15.6 −1.9 −5.2 42.3

16.7 −3.5 −9.2 43.8

15 13.1 −3.2 43.5

Coupler Base L* a* b* ΔE_(ab)*

26.2 1.5 4.9 33.3

25.1 −1.2 5.3 29.6

17.3 18.9 1.5 42

The build-ups of the dyes are significantly higher than that obtainedwith a standard oxidation dye support.

The invention claimed is:
 1. Composition for dyeing keratin fibres,characterized in that it comprises: i) one or more fatty substances, ii)one or more surfactants, iii) one or more oxidation bases, iv) one ormore basifying agents, v) one or more meta-phenylenediamine-basedcouplers of formula (I), and also the addition salts thereof, opticalisomers, geometrical isomers and tautomers thereof, or solvates thereof:

in which formula (I): R₁ represents a linear or branched C₁-C₆ alkylradical, which may be substituted with one or more of the following:—CONH₂ radicals, —NHCOCH₃ radicals, —NHSO₂CH₃ radicals,di(C₁-C₆)alkylamino radicals, hydroxyl radicals, amino radicals, —COOHradicals, R₂ represents: a hydrogen atom, a linear or branched C₁-C₆alkyl radical, which may be substituted with one or more of thefollowing: —CONH₂ radicals, —NHSO₂CH₃ radicals, di(C₁-C₆)alkylaminoradicals, hydroxyl radicals, amino radicals, —COOH radicals, C₁-C₆alkoxy radicals, a linear or branched C₁-C₆ alkoxy radical, which may besubstituted with one or more of the following: —CONH₂ radicals,—NHSO₂CH₃ radicals, di(C₁-C₆)alkylamino radicals, hydroxyl radicals,amino radicals, —COOH radicals, C₁-C₆ alkoxy radicals, a halogenradical, R₃ and R₄ represent, independently of each other: a hydrogenatom, a linear or branched C₁-C₆ alkyl radical, which may be substitutedwith one or more of the following: di(C₁-C₆)alkylamino radicals,hydroxyl radicals, amino radicals, C₁-C₆ alkoxy radicals, X representsan oxygen or sulfur atom, n represents an integer ranging from 0 to 2,(vi) one or more chemical oxidizing agents, the fatty substance contentrepresenting in total at least 15% by weight relative to the totalweight of the said dye composition.
 2. Dye composition according toclaim 1, characterized in that the fatty substance(s) are chosen fromC₆-C₁₆ hydrocarbons, hydrocarbons containing more than 16 carbon atoms,non-silicone oils of animal origin, triglycerides of plant or syntheticorigin, fluoro oils, fatty alcohols, fatty acid esters other thantriglycerides and non-silicone waxes, fatty alcohol esters other thantriglycerides and non-silicone waxes, non-silicone waxes, and silicones,and mixtures thereof.
 3. Dye composition according to claim 1,characterized in that it comprises at least 20% by weight of fattysubstance relative to the weight of the composition.
 4. Dye compositionaccording to claim 1, characterized in that the surfactants are chosenfrom nonionic surfactants.
 5. Dye composition according to claim 1,characterized in that the oxidation bases are chosen frompara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,ortho-aminophenols, heterocyclic bases, and the addition salts thereof,and solvates thereof.
 6. Dye composition according to claim 1,characterized in that the meta-phenylenediamine-based couplers arechosen from those of formula (I) in which R₁ represents a linear C₁-C₄alkyl radical, optionally substituted with one or more hydroxyl groups,an amino group or a group —NHCOCH₃.
 7. Dye composition according toclaim 1, characterized in that the meta-phenylenediamine-based couplersare chosen from those of formula (I) in which R₃ and R₄ represent,independently of each other, a hydrogen atom or a linear C₁-C₆ alkylradical, optionally substituted with a hydroxyl group.
 8. Dyecomposition according to claim 1, characterized in that themeta-phenylenediamine-based couplers of formula (I) are chosen from thefollowing compounds, the addition salts thereof, optical isomers,geometrical isomers and tautomers thereof, and solvates thereof:


9. Dye composition according to claim 1, characterized in thatcoupler(s) are chosen from couplers (1) and (2), and also the additionsalts thereof, optical isomers, geometrical isomers and tautomersthereof, and solvates thereof.
 10. Dye composition according to claim 1,characterized in that the basifying agent(s) are mineral, organic orhybrid, chosen from aqueous ammonia, alkali metal carbonates orbicarbonates, sodium hydroxide, potassium hydroxide, organic amineschosen from alkanolamines, oxyethylenated and/or oxypropylenatedethylenediamines, amino acids and the compounds of formula (II) andmixtures thereof:

in which formula (II) W is a divalent C₁-C₆ alkylene radical optionallysubstituted with one or more hydroxyl groups or a C₁-C₆ alkyl radical,optionally interrupted with one or more heteroatoms such as O, orNR_(u), R_(x), R_(y), R_(z), R_(t) and R_(u), which may be identical ordifferent, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆hydroxyalkyl or C₁-C₆ aminoalkyl radical.
 11. Dye composition accordingto claim 1, characterized in that the basifying agents are chosen fromalkanolamines and amino acids in neutral or ionic form.
 12. Dyecomposition according to claim 1, characterized in that it comprises atleast hydrogen peroxide as chemical oxidizing agent.
 13. Process fordyeing keratin fibres, which consists in applying to the said fibres adye composition as defined according to claim
 1. 14. Dyeing processaccording to claim 13, characterized in that the composition resultsfrom the extemporaneous mixing of two compositions; a composition (A)comprising one or more oxidation bases, one or moremeta-phenylenediamine-based couplers of formula (I) and one or morebasifying agents, and a composition (B) comprising one or more chemicaloxidizing agents, at least one of the compositions (A) and (B)comprising one or more fatty substances and one or more surfactants; thefatty substance content of the composition resulting from theextemporaneous mixing of compositions (A) and (B) corresponding to atleast 15% by weight of fatty substance.
 15. Process according to claim14, characterized in that the composition results from theextemporaneous mixing of three compositions; two aqueous compositions(B′) and (C′) and an anhydrous composition (A′), the anhydrouscomposition (A′) comprising one or more fatty substances, thecomposition (B′) comprising one or more oxidation bases and one or moremeta-phenylenediamine-based couplers of formula (I), the composition(C′) comprising one or more chemical oxidizing agents, one or morebasifying agents being included in the compositions (A′) and/or (B′) andpreferably only in composition (B′), one or more surfactants beingincluded in at least one of the compositions (A′), (B′) and (C′), thefatty substance content of the composition resulting from theextemporaneous mixing of the three compositions (A′), (B′) and (C′)representing at least 15% by weight of fatty substance. 16.Multi-compartment device comprising a first compartment containingcomposition (A) as described in claim 14 and at least a secondcompartment containing composition (B) as described in claim 14, thecompositions of the compartments being intended to be mixed togetherbefore application, on condition that the amount of fatty substancerepresents at least 15% by weight relative to the weight of thecomposition resulting from the mixing of (A) and (B). 17.Multi-compartment device comprising a first compartment containingcomposition (A′) as described in claim 15; and a second compartmentcontaining a cosmetic composition (B′) as described in claim 15 and atleast a third compartment comprising composition (C′) as described inclaim 15; the compositions of the compartments being intended to bemixed together before application, on condition that the amount of fattysubstance represents at least 15% by weight relative to the weight ofthe composition resulting from the mixing of (A′), (B′) and (C′). 18.Dye composition according to claim 2, characterized in that the fattysubstance(s) are chosen from liquid petroleum jelly, C₆-C₁₆ alkanes,polydecenes, liquid esters of fatty acids other than triglycerides,liquid esters of fatty alcohols other than triglycerides, and liquidfatty alcohols, and mixtures thereof.
 19. Dye composition according toclaim 4, characterized in that the nonionic surfactants are chosen frommonooxyalkylenated or polyoxyalkylenated nonionic surfactants,monoglycerolated or polyglycerolated nonionic surfactants, andalkylpolyglucosides, and mixtures thereof.
 20. Dye composition accordingto claim 6, characterized in that the meta-phenylenediamine-basedcouplers are chosen from those of formula (I) in which R₁ represents aC₁ alkyl radical, optionally substituted with one or more hydroxylgroups, an amino group or a group —NHCOCH₃.